Simple Monomers for Precise Polymer Functionalization During Ring-Opening Metathesis Polymerization

Foster, Jeffrey C.; Damron, Joshua T.; Zhang, Honghai

doi:10.1021/acs.macromol.3c01068

Title: Simple Monomers for Precise Polymer Functionalization During Ring-Opening Metathesis Polymerization

Journal Article · 20 September 2023 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.3c01068 · OSTI ID:2001360

^[1];

^[2]

Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Controlling the monomer sequence of synthetic polymers is a grand challenge in polymer science. Conventional sequence control has been achieved in dispersed polymers by exploiting the kinetic tendencies of monomers and their order of addition. While the sequence of blocks in multiblock copolymers can be readily tuned using sequential addition of monomers (SAM), control over the sequence distribution is eroded as the targeted block size approaches a single monomer unit (i.e., X_n ~ 1) due to the stochastic nature of chain-growth reactions. Thus, unique monomers are needed to ensure precise single additions. Herein, we investigate common classes of cyclic olefin monomers for ring-opening metathesis polymerization (ROMP) to identify monomers for single unit addition during sequential monomer addition synthesis. Through careful analysis of polymerization kinetics, we find that easily synthesized oxanorbornene imide monomers are suitable for single-addition reactions. With the identified monomers, we demonstrate the synthesis of multiblock copolymers containing up to three precise functionalization sites and singly cross-linked four-armed star copolymers. In conclusion, we envision that expanded kinetic analyses of monomer reactivities in ROMP reactions will enable novel polymer synthesis capabilities such as the autonomous synthesis of sequence-defined polymers or one-shot multiblock copolymer syntheses.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2001360

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 19 Vol. 56; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (68)

Synthesis of A,B-Alternating Copolymers by Ring-Opening-Insertion-Metathesis Polymerization Choi, Tae-Lim; Rutenberg, Isaac M.; Grubbs, Robert H. Angewandte Chemie International Edition, Vol. 41, Issue 20 https://doi.org/10.1002/1521-3773(20021018)41:20<3839::AID-ANIE3839>3.0.CO;2-H	journal	October 2002
Precision Synthesis of Biodegradable Polymers Thomas, Christophe M.; Lutz, Jean-François Angewandte Chemie International Edition, Vol. 50, Issue 40 https://doi.org/10.1002/anie.201103076	journal	July 2011
Control of a Living Radical Polymerization of Methacrylates by Light Fors, Brett P.; Hawker, Craig J. Angewandte Chemie International Edition, Vol. 51, Issue 35 https://doi.org/10.1002/anie.201203639	journal	July 2012
Towards Sequence-Controlled Antimicrobial Polymers: Effect of Polymer Block Order on Antimicrobial Activity Judzewitsch, Peter R.; Nguyen, Thuy-Khanh; Shanmugam, Sivaprakash Angewandte Chemie International Edition, Vol. 57, Issue 17 https://doi.org/10.1002/anie.201713036	journal	March 2018
Degradation in Order: Simple and Versatile One‐Pot Combination of Two Macromolecular Concepts to Encode Diverse and Spatially Regulated Degradability Functions Fuoco, Tiziana Angewandte Chemie International Edition, Vol. 60, Issue 28 https://doi.org/10.1002/anie.202103143	journal	June 2021
Self-assembly of peptide amphiphiles: From molecules to nanostructures to biomaterials Cui, Honggang; Webber, Matthew J.; Stupp, Samuel I. Biopolymers, Vol. 94, Issue 1, p. 1-18 https://doi.org/10.1002/bip.21328	journal	January 2010
Single-Chain Folding of Synthetic Polymers: A Critical Update Altintas, Ozcan; Barner-Kowollik, Christopher Macromolecular Rapid Communications, Vol. 37, Issue 1 https://doi.org/10.1002/marc.201500547	journal	November 2015
Selective single monomer addition in living cationic polymerization: Sequential double end-functionalization in combination with capping agent Ida, Shohei; Terashima, Takaya; Ouchi, Makoto Journal of Polymer Science Part A: Polymer Chemistry, Vol. 48, Issue 15 https://doi.org/10.1002/pola.24122	journal	June 2010
Precise Placement of Single Monomer Units in Living Ring-Opening Metathesis Polymerization Elling, Benjamin R.; Su, Jessica K.; Feist, John D. Chem, Vol. 5, Issue 10 https://doi.org/10.1016/j.chempr.2019.07.017	journal	October 2019
Radical-promoted single-unit monomer insertion (SUMI) [aka. reversible-deactivation radical addition (RDRA)] Boyer, Cyrille; Kamigaito, Masami; Satoh, Kotaro Progress in Polymer Science, Vol. 138 https://doi.org/10.1016/j.progpolymsci.2023.101648	journal	March 2023
Access to Bicyclo[4.2.0]octene Monomers To Explore the Scope of Alternating Ring-Opening Metathesis Polymerization Chen, Lei; Li, Liqiang; Sampson, Nicole S. The Journal of Organic Chemistry, Vol. 83, Issue 5 https://doi.org/10.1021/acs.joc.8b00054	journal	February 2018
User Guide to Ring-Opening Metathesis Polymerization of endo-Norbornene Monomers with Chelated Initiators Cater, Henry L.; Balynska, Iana; Allen, Marshall J. Macromolecules, Vol. 55, Issue 15 https://doi.org/10.1021/acs.macromol.2c01196	journal	July 2022
Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene Leguizamon, Samuel C.; Monk, Nicolas T.; Hochrein, Madison T. Macromolecules, Vol. 55, Issue 18 https://doi.org/10.1021/acs.macromol.2c01244	journal	September 2022
What Is Next in Single-Chain Nanoparticles? Hanlon, Ashley M.; Lyon, Christopher K.; Berda, Erik B. Macromolecules, Vol. 49, Issue 1 https://doi.org/10.1021/acs.macromol.5b01456	journal	December 2015
Simple and Accurate Determination of Reactivity Ratios Using a Nonterminal Model of Chain Copolymerization Beckingham, Bryan S.; Sanoja, Gabriel E.; Lynd, Nathaniel A. Macromolecules, Vol. 48, Issue 19 https://doi.org/10.1021/acs.macromol.5b01631	journal	September 2015
Sequence Effects on Block Copolymer Self-Assembly through Tuning Chain Conformation and Segregation Strength Utilizing Sequence-Defined Polypeptoids Patterson, Anastasia L.; Danielsen, Scott P. O.; Yu, Beihang Macromolecules, Vol. 52, Issue 3 https://doi.org/10.1021/acs.macromol.8b02298	journal	January 2019
Single Unit Monomer Insertion: A Versatile Platform for Molecular Engineering through Radical Addition Reactions and Polymerization Xu, Jiangtao Macromolecules, Vol. 52, Issue 23 https://doi.org/10.1021/acs.macromol.9b01365	journal	October 2019
Controlled Alternating Metathesis Copolymerization of Terminal Alkynes Pal, Subhajit; Mandal, Indradip; Kilbinger, Andreas F. M. ACS Macro Letters, Vol. 11, Issue 7 https://doi.org/10.1021/acsmacrolett.2c00258	journal	June 2022
Sequence-Controlled Copolymers Prepared via Entropy-Driven Ring-Opening Metathesis Polymerization Weiss, Ryan M.; Short, Amy L.; Meyer, Tara Y. ACS Macro Letters, Vol. 4, Issue 9 https://doi.org/10.1021/acsmacrolett.5b00528	journal	September 2015
Iterative Radical Addition with a Special Monomer Carrying Bulky and Convertible Pendant: A New Concept toward Controlling the Sequence for Vinyl Polymers Oh, Dongyoung; Ouchi, Makoto; Nakanishi, Tomoya ACS Macro Letters, Vol. 5, Issue 6 https://doi.org/10.1021/acsmacrolett.6b00359	journal	May 2016
Tapered Bottlebrush Polymers: Cone-Shaped Nanostructures by Sequential Addition of Macromonomers Radzinski, Scott C.; Foster, Jeffrey C.; Scannelli, Samantha J. ACS Macro Letters, Vol. 6, Issue 10 https://doi.org/10.1021/acsmacrolett.7b00724	journal	October 2017
Efficient and Facile End Group Control of Living Ring-Opening Metathesis Polymers via Single Addition of Functional Cyclopropenes Elling, Benjamin R.; Xia, Yan ACS Macro Letters, Vol. 7, Issue 6 https://doi.org/10.1021/acsmacrolett.8b00347	journal	May 2018
Antibacterial Studies of Cationic Polymers with Alternating, Random, and Uniform Backbones Song, Airong; Walker, Stephen G.; Parker, Kathlyn A. ACS Chemical Biology, Vol. 6, Issue 6 https://doi.org/10.1021/cb100413w	journal	March 2011
Molecular Weight Control by a "Living" Free-Radical Polymerization Process Hawker, Craig J. Journal of the American Chemical Society, Vol. 116, Issue 24 https://doi.org/10.1021/ja00103a055	journal	November 1994
Controlled/"living" radical polymerization. atom transfer radical polymerization in the presence of transition-metal complexes Wang, Jin-Shan; Matyjaszewski, Krzysztof Journal of the American Chemical Society, Vol. 117, Issue 20 https://doi.org/10.1021/ja00125a035	journal	May 1995
Titanacyclobutanes derived from strained, cyclic olefins: the living polymerization of norbornene Gilliom, Laura R.; Grubbs, Robert H. Journal of the American Chemical Society, Vol. 108, Issue 4 https://doi.org/10.1021/ja00264a027	journal	February 1986
Solid Phase Peptide Synthesis. I. The Synthesis of a Tetrapeptide Merrifield, R. B. Journal of the American Chemical Society, Vol. 85, Issue 14, p. 2149-2154 https://doi.org/10.1021/ja00897a025	journal	July 1963
POLYMERIZATION INITIATED BY ELECTRON TRANSFER TO MONOMER. A NEW METHOD OF FORMATION OF BLOCK POLYMERS ¹ Szwarc, M.; Levy, M.; Milkovich, R. Journal of the American Chemical Society, Vol. 78, Issue 11 https://doi.org/10.1021/ja01592a101	journal	June 1956
Scope of the Ring-Opening Metathesis Polymerization (ROMP) Reaction of 1-Substituted Cyclobutenes Song, Airong; Lee, Jae Chul; Parker, Kathlyn A. Journal of the American Chemical Society, Vol. 132, Issue 30 https://doi.org/10.1021/ja1037098	journal	August 2010
Exploiting Sequence To Control the Hydrolysis Behavior of Biodegradable PLGA Copolymers Li, Jian; Stayshich, Ryan M.; Meyer, Tara Y. Journal of the American Chemical Society, Vol. 133, Issue 18 https://doi.org/10.1021/ja200895s	journal	May 2011
The Effect of Monomer Order on the Hydrolysis of Biodegradable Poly(lactic- co -glycolic acid) Repeating Sequence Copolymers Li, Jian; Rothstein, Sam N.; Little, Steven R. Journal of the American Chemical Society, Vol. 134, Issue 39 https://doi.org/10.1021/ja306866w	journal	September 2012
A Robust and Versatile Photoinduced Living Polymerization of Conjugated and Unconjugated Monomers and Its Oxygen Tolerance Xu, Jiangtao; Jung, Kenward; Atme, Amir Journal of the American Chemical Society, Vol. 136, Issue 14 https://doi.org/10.1021/ja501745g	journal	February 2014
Synthesis of Copolymers by Alternating ROMP (AROMP) Song, Airong; Parker, Kathlyn A.; Sampson, Nicole S. Journal of the American Chemical Society, Vol. 131, Issue 10 https://doi.org/10.1021/ja809661k	journal	March 2009
Alternating Cascade Metathesis Polymerization of Enynes and Cyclic Enol Ethers with Active Ruthenium Fischer Carbenes Sui, Xuelin; Zhang, Tianqi; Pabarue, Alec B. Journal of the American Chemical Society, Vol. 142, Issue 30 https://doi.org/10.1021/jacs.0c06045	journal	July 2020
Living Anionic Addition Reaction of 1,1-Diphenylethylene Derivatives: One-Pot Synthesis of ABC-type Chain-End Sequence-Controlled Polymers Takahata, Kazuki; Aizawa, Naoki; Nagao, Masashi Journal of the American Chemical Society, Vol. 143, Issue 30 https://doi.org/10.1021/jacs.1c04500	journal	July 2021
The Fluorocarbene Exploit: Enforcing Alternation in Ring-Opening Metathesis Polymerization Tashiro, Kaoru; Akiyama, Midori; Kashiwagi, Kimiaki Journal of the American Chemical Society, Vol. 145, Issue 5 https://doi.org/10.1021/jacs.2c11373	journal	January 2023
Cationic Single-Unit Monomer Insertion (cSUMI): From Discrete Oligomers to the α-/ω-End and In-Chain Sequence-Regulated Polymers Tao, Wei; He, Wei; Feng, Xuepu Journal of the American Chemical Society, Vol. 145, Issue 6 https://doi.org/10.1021/jacs.2c12873	journal	February 2023
Synthesis of Non-Natural Sequence-Encoded Polymers Using Phosphoramidite Chemistry Al Ouahabi, Abdelaziz; Charles, Laurence; Lutz, Jean-François Journal of the American Chemical Society, Vol. 137, Issue 16 https://doi.org/10.1021/jacs.5b02639	journal	April 2015
A General Approach to Sequence-Controlled Polymers Using Macrocyclic Ring Opening Metathesis Polymerization Gutekunst, Will R.; Hawker, Craig J. Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b04940	journal	June 2015
Living Alternating Ring-Opening Metathesis Polymerization Based on Single Monomer Additions Elling, Benjamin R.; Xia, Yan Journal of the American Chemical Society, Vol. 137, Issue 31 https://doi.org/10.1021/jacs.5b05497	journal	July 2015
Bottlebrush Polymer Synthesis by Ring-Opening Metathesis Polymerization: The Significance of the Anchor Group Radzinski, Scott C.; Foster, Jeffrey C.; Chapleski, Robert C. Journal of the American Chemical Society, Vol. 138, Issue 22 https://doi.org/10.1021/jacs.5b13317	journal	May 2016
Beyond Dispersity: Deterministic Control of Polymer Molecular Weight Distribution Gentekos, Dillon T.; Dupuis, Lauren N.; Fors, Brett P. Journal of the American Chemical Society, Vol. 138, Issue 6 https://doi.org/10.1021/jacs.5b13565	journal	February 2016
Control of Grafting Density and Distribution in Graft Polymers by Living Ring-Opening Metathesis Copolymerization Lin, Tzu-Pin; Chang, Alice B.; Chen, Hsiang-Yun Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.7b00791	journal	March 2017
Design, Synthesis, and Self-Assembly of Polymers with Tailored Graft Distributions Chang, Alice B.; Lin, Tzu-Pin; Thompson, Niklas B. Journal of the American Chemical Society, Vol. 139, Issue 48 https://doi.org/10.1021/jacs.7b10525	journal	November 2017
Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers Sternhagen, Garrett L.; Gupta, Sudipta; Zhang, Yueheng Journal of the American Chemical Society, Vol. 140, Issue 11 https://doi.org/10.1021/jacs.8b00461	journal	February 2018
Self-Assembled Nanostructures Regulate H ₂ S Release from Constitutionally Isomeric Peptides Wang, Yin; Kaur, Kuljeet; Scannelli, Samantha J. Journal of the American Chemical Society, Vol. 140, Issue 44 https://doi.org/10.1021/jacs.8b09320	journal	October 2018
Examining the Effects of Monomer and Catalyst Structure on the Mechanism of Ruthenium-Catalyzed Ring-Opening Metathesis Polymerization Wolf, William J.; Lin, Tzu-Pin; Grubbs, Robert H. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b08835	journal	October 2019
Mechanistic and Kinetic Studies of the Ring Opening Metathesis Polymerization of Norbornenyl Monomers by a Grubbs Third Generation Catalyst Hyatt, Michael G.; Walsh, Dylan J.; Lord, Richard L. Journal of the American Chemical Society, Vol. 141, Issue 44 https://doi.org/10.1021/jacs.9b09752	journal	October 2019
Polymerization of Methyl Methacrylate with the Carbon Tetrachloride/Dichlorotris- (triphenylphosphine)ruthenium(II)/Methylaluminum Bis(2,6-di-tert-butylphenoxide) Initiating System: Possibility of Living Radical Polymerization Kato, Mitsuru; Kamigaito, Masami; Sawamoto, Mitsuo Macromolecules, Vol. 28, Issue 5 https://doi.org/10.1021/ma00109a056	journal	September 1995
Sequence-regulated oligomers and polymers by living cationic polymerization. 2. Principle of sequence regulation and synthesis of sequence-regulated oligomers of functional vinyl ethers and styrene derivatives Minoda, Masahiko; Sawamoto, Mitsuo; Higashimura, Toshinobu Macromolecules, Vol. 23, Issue 23 https://doi.org/10.1021/ma00225a001	journal	November 1990
Pushing the Limit of the RAFT Process: Multiblock Copolymers by One-Pot Rapid Multiple Chain Extensions at Full Monomer Conversion Gody, Guillaume; Maschmeyer, Thomas; Zetterlund, Per B. Macromolecules, Vol. 47, Issue 10 https://doi.org/10.1021/ma402435n	journal	May 2014
Living Free-Radical Polymerization by Reversible Addition−Fragmentation Chain Transfer: The RAFT Process Chiefari, John; Chong, Y. K. (Bill); Ercole, Frances Macromolecules, Vol. 31, Issue 16 https://doi.org/10.1021/ma9804951	journal	August 1998
Synthesis of Sequence-Specific Vinyl Copolymers by Regioselective ROMP of Multiply Substituted Cyclooctenes Zhang, Jihua; Matta, Megan E.; Hillmyer, Marc A. ACS Macro Letters, Vol. 1, Issue 12 https://doi.org/10.1021/mz300535r	journal	November 2012
Iterative exponential growth of stereo- and sequence-controlled polymers Barnes, Jonathan C.; Ehrlich, Deborah J. C.; Gao, Angela X. Nature Chemistry, Vol. 7, Issue 10 https://doi.org/10.1038/nchem.2346	journal	September 2015
Controlled folding of synthetic polymer chains through the formation of positionable covalent bridges Schmidt, Bernhard V. K. J.; Fechler, Nina; Falkenhagen, Jana Nature Chemistry, Vol. 3, Issue 3 https://doi.org/10.1038/nchem.964	journal	January 2011
A strategy for sequence control in vinyl polymers via iterative controlled radical cyclization Hibi, Yusuke; Ouchi, Makoto; Sawamoto, Mitsuo Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms11064	journal	March 2016
Advances in heterometallic ring-opening (co)polymerisation catalysis Gruszka, Weronika; Garden, Jennifer A. Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23192-y	journal	May 2021
Synthesis of sequence controlled acrylate oligomers via consecutive RAFT monomer additions Vandenbergh, Joke; Reekmans, Gunter; Adriaensens, Peter Chemical Communications, Vol. 49, Issue 88 https://doi.org/10.1039/C3CC45994B	journal	January 2013
Precision polymers: a kinetic approach for functional poly(norbornenes) Moatsou, Dafni; Hansell, Claire F.; O'Reilly, Rachel K. Chem. Sci., Vol. 5, Issue 6 https://doi.org/10.1039/C4SC00752B	journal	January 2014
AB-alternating copolymers via chain-growth polymerization: synthesis, characterization, self-assembly, and functions Nishimori, Kana; Ouchi, Makoto Chemical Communications, Vol. 56, Issue 24 https://doi.org/10.1039/D0CC00275E	journal	January 2020
Oxanorbornenes: promising new single addition monomers for the metathesis polymerization Pal, Subhajit; Alizadeh, Mahshid; Kong, Phally Chemical Science, Vol. 12, Issue 19 https://doi.org/10.1039/D1SC00036E	journal	January 2021
Sequence control in polymer synthesis Badi, Nezha; Lutz, Jean-François Chemical Society Reviews, Vol. 38, Issue 12 https://doi.org/10.1039/b806413j	journal	January 2009
Sequence-controlled polymerizations: the next Holy Grail in polymer science? Lutz, Jean-François Polymer Chemistry, Vol. 1, Issue 1 https://doi.org/10.1039/b9py00329k	journal	January 2010
Scalable synthesis of sequence-defined, unimolecular macromolecules by Flow-IEG Leibfarth, Frank A.; Johnson, Jeremiah A.; Jamison, Timothy F. Proceedings of the National Academy of Sciences, Vol. 112, Issue 34 https://doi.org/10.1073/pnas.1508599112	journal	August 2015
Macromolecules with programmable shape, size, and chemistry Walsh, Dylan J.; Guironnet, Damien Proceedings of the National Academy of Sciences, Vol. 116, Issue 5 https://doi.org/10.1073/pnas.1817745116	journal	January 2019
Computationally designed peptides for self-assembly of nanostructured lattices Zhang, Huixi Violet; Polzer, Frank; Haider, Michael J. Science Advances, Vol. 2, Issue 9 https://doi.org/10.1126/sciadv.1600307	journal	September 2016
Sequence-Controlled Polymers Lutz, J. -F.; Ouchi, M.; Liu, D. R. Science, Vol. 341, Issue 6146 https://doi.org/10.1126/science.1238149	journal	August 2013
Anionic Copolymerization of Styrene and 1, 1-Diphenylethylene Yuki, Heimei; Hotta, Junichi; Okamoto, Yoshio Bulletin of the Chemical Society of Japan, Vol. 40, Issue 11 https://doi.org/10.1246/bcsj.40.2659	journal	November 1967

Similar Records

Impacts of Disulfide‐Containing Monomers in Alternating Diene Metathesis Polymerization

Journal Article · 2025 · Journal of Polymer Science · OSTI ID:2574184

Lee, Kyoungwon; Russell, Thomas P; Emrick, Todd

Functionalized block copolymers as adhesion promoters

Conference · 1995 · OSTI ID:32517

Kent, M S; Saunders, R

Ring-opening metathesis polymerization of cobaltocenium derivative to prepare anion exchange membrane with high ionic conductivity

Journal Article · 2020 · Polyhedron · OSTI ID:1774250

Yuan, Haomiao; Liu, Ye; Tsai, Tsung-Han; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
copolymerization
copolymers
monomers
nuclear magnetic resonance spectroscopy
polymers

Title: Simple Monomers for Precise Polymer Functionalization During Ring-Opening Metathesis Polymerization

Citation Formats

References (68)

Similar Records

Related Subjects